H+-selective electrodes based on neutral carriers: Specific features in behaviour and quantitative description of the electrode response

Егоров, В. В.; Lushchik, Ya. F.

doi:10.1016/0039-9140(90)80071-m

Cited by 37 publications

(29 citation statements)

References 10 publications

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“…The effect of the nature of the anion on the TBA based SCE was strongest in SCN 7 , I 7 , least in NO 3 À , Br 7 and Cl 7 . Their anion interference imposes limitation in their use in acidic solution, because it was formed as a more stable complex as noted above [37].…”

Section: Resultsmentioning

confidence: 99%

All Solid State Hydrogen Ion Selective Electrode Based on a Tribenzylamine Neutral Carrier in a Poly(vinyl chloride) Membrane with a Poly(aniline) Solid Contact

et al. 2001

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Section: Resultsmentioning

confidence: 99%

All Solid State Hydrogen Ion Selective Electrode Based on a Tribenzylamine Neutral Carrier in a Poly(vinyl chloride) Membrane with a Poly(aniline) Solid Contact

et al. 2001

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“…Similar observations have been reported by Simon et al 15,16 The small pH dependence at high and/or low pH regions, observed for all membranes, is likely to be due to cation and/or anion interference, respectively. 17,18 On the other hand, the pH dependence of membrane 3 based on trihexylamine (3) was negligible, similarly as the blank membrane containing no particular sensory element. The absence of an appreciable pH dependence of membrane 3 can be explained by a lack of the ability of 3 to uptake protons into the membrane phase, due to insufficient lipophilicity.…”

Section: Membranes 1 -5 Based On Aliphatic Aminesmentioning

confidence: 99%

A Variety of Lipophilic Amines Incorporated in Liquid Membranes Exhibit Potentiometric Responses to Neutral Phenols

et al. 1998

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In a preceding paper 1 we reported on a systematic study of potentiometric responses to neutral phenols (ArOH) by poly(vinyl chloride) (PVC) matrix liquid membranes based on quaternary ammonium or phosphonium salts (Q + X -), and proposed a new model for the observed anionic responses. In this model, the decrease in the amount of Q + and X -that are chargeseparated across the membrane interface is explained on the basis of the following two processes: (i) Complexation of Q + X -and the extracted ArOH, leading to a net movement of anionic species (X -) from the aqueous to the membrane phase. (ii) Proton dissociation of the complexed ArOH and concomitant ejection of HX into the aqueous phase, involving a net movement of cationic species (H + ) from the membrane to the aqueous phase. A theoretical treatment based on the above model reproduced the potentiometric response behaviors for undissociated phenols. This model was further supported by optical second harmonic generation (SHG), which enabled a direct observation of the processes occurring at the interface of a liquid membrane and an aqueous solution.Based on the findings of Kimura et al.2 that a macrocyclic polyamine forms complexes with neutral phenols in aqueous solutions, we previously examined potentiometric responses to phenols by a PVC matrix liquid membrane based on lipophilic macrocyclic pentaamine 1, and found that the membrane exhibits anionic responses to undissociated, neutral phenols.3,4 This response behavior is quite similar to that observed for PVC matrix liquid membranes based on quaternary ammonium or phosphonium salts. A variety of lipophilic amines incorporated in PVC matrix liquid membranes exhibited anionic potentiometric responses to phenolic compounds at the pH conditions under which the phenols exist mainly or exclusively in their undissociated, neutral forms. The examined lipophilic amines include a macrocyclic pentaamine, tri(decyl)amine, 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline), 4-octadecylpyridine, and sapphyrin. The potentiometric selectivities of the membranes based on lipophilic aliphatic amines (B) reflected the acidity (hydrogen bond donor activity) and lipophilicity (extractability) of the phenols (ArOH), similarly as membranes based on lipophilic quaternary ammonium salts (Q + X -). The anionic responses were explained on the basis of a decrease in the charge separation of protonated amines (BH + ) and their counteranions (X -) across the membrane interface. Possible processes leading to a decrease in the charge separation between BH + and X -are (i) complexation between ArOH and BH + X -, followed by proton dissociation and ejection of HX into the aqueous phase, as well as (ii) complexation between ArOH and B. The membrane based on sapphyrin showed a high potentiometric selectivity to catechol, possibly due to geometrical discrimination of the ortho dihydroxy structure of catechol by the nitrogen(s) on the rigid macrocyclic structure of sapphyrin.

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“…[8][9][10][11][12][13][14] However, the equations describing the relationship between the ionic site concentrations and the response slopes, which is important for the membrane preparation, have not been reported yet. In addition, to experimentally confirm the validity of the Donnan failure theory, many investigators have measured potentiometric responses to primary ions with solvent polymeric membranes.…”

Section: Introductionmentioning

confidence: 99%

Threshold Ionic Site Concentrations Required for Nernstian Potentiometric Responses of Neutral Ionophore-Incorporated Ion-Selective Liquid Membranes

et al. 2001

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An equation that can describe the concentrations of ionic sites required for a Nernstian potentiometric response slope of neutral ionophore-incorporated ion-selective liquid membranes is presented. This equation is derived from a model based on electrical diffuse layers on both the membrane and the aqueous sides of the interface, in which the phase boundary potential is correlated to the surface charge density as well as the salt concentrations in the bulk membrane and aqueous solution. To experimentally and accurately confirm the validity of this equation, response characteristics of field effect transistors covered by neutral ionophore-based liquid membranes with varying concentrations of a derivative of tetraphenylborate as an anionic site but free of ionic impurities were examined. The observed membrane potentials and the response slopes for membranes with various concentrations of anionic sites were in good agreement with the values calculated from the theory presented in this paper with the measured complexation stability constants for the relevant systems. This result indicates that the theoretical prediction based on the proposed equation for the anionic site concentration is accessible for the preparation of neutral ionophore-incorporated ion-selective liquid membranes, which show Nernstian response slopes for the primary ions.

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H+-selective electrodes based on neutral carriers: Specific features in behaviour and quantitative description of the electrode response

Cited by 37 publications

References 10 publications

All Solid State Hydrogen Ion Selective Electrode Based on a Tribenzylamine Neutral Carrier in a Poly(vinyl chloride) Membrane with a Poly(aniline) Solid Contact

All Solid State Hydrogen Ion Selective Electrode Based on a Tribenzylamine Neutral Carrier in a Poly(vinyl chloride) Membrane with a Poly(aniline) Solid Contact

A Variety of Lipophilic Amines Incorporated in Liquid Membranes Exhibit Potentiometric Responses to Neutral Phenols

Threshold Ionic Site Concentrations Required for Nernstian Potentiometric Responses of Neutral Ionophore-Incorporated Ion-Selective Liquid Membranes

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